Process of chlorinating and products thereof.



G. MERSEREAU.

PROCESS OF GHLORINATING AND PRODUCTS THEREOF.

APPLICATION FILED MAR. 21. 1913.

- L2AS5 Patented May 1, 1917.

' snares ran cano GAIL MEBSEREAU, OF NEW YORK, N. Y., ASSIGNOR TOCHEMICAL DEVELOPMENT COMPANY, A CORPORATION OF MAINE.

Specification of Letters Patent.

Patented May 11, 1917.

Application filed March 27, 1913. Serial No. 757,146.

To all whom it may concern:

Be it known that I, GAILVBIERSEREAU, a

citizen of the United States, residing at New York, in the county of NewYork and State of New York, have invented certain new and usefulImprovements in Processes of Chlorinating and Products Thereof, of whichthe following is a specification.

This invention relates to processes of chlorinating and productsthereof; and it comprises a method wherein heavy -petroleum oil ispassed through a heated zone at a temperature and a rate of speedsulficient to give a substantial proportion of gases and a substantialproportion of unchanged heavy oil, the gas is cooled and the unchangedoil is removed carrying with it low -boiling' bodies, the purified gasis advantageously mixed with successive proportions of chlorin atvarying temperatures advantageously in one or more dark chambers, andthe carbon chlorids condensed. The condensate may be only about 10pounds per gallon or a specific gravity of about 1.2, containing about70 per cent. chlorin and consisting of a mixture of organic chloridscontaining ethylene and propylene dichlorids in a ratio of about 2 :1;all as more full-y hereinafter set forth and as claimed.

For many purposes, as in the extraction of oil and grease from oilseeds, such as cottonseed, linseed, etc., from fish, from dress goods,from wool, etc., it is desirable to have a substantially uninflammable,easilyvolatile liquid which is a good solvent for oil and grease and isreadily. evaporated, distilled, recovered or handled without risk offire. Carbon tetrachlorid is generally used for this purpose and hasmany advantages; but it is expensive to make, and the manufacture is byno means cheap or free of danger since it is generally manufactured fromcarbon bisulfid as a raw material. Its heaviness is also against itsince a gallon weighs in exccss of 13 pounds. High density is of courseno advantage in an oil solvent. Further, it contains 92 per cent.chlorin which is much more than is necessary to make a materialsubstantially uninflammable. This excessive amount of chlorin also addsto the expense of manufacture. The odor of the tetrachlorid is alsostrong, and, to many people, unpleasant. Chloroform is more expensivethan the tetrachlorid and for this reason and because of itscharacteristic odor it is not used commercially as a grease solvent. Inthe art, elforts have bee-n made to lighten and cheapencarbontetrachlorid by mixing it with more or less gasolene or othervolatile hydrocarbons which are lighter, cheaper substances; mixtures ofthis sort being Well known inthe trade as grease removers for garments.Unfortunately these admixtures with inflammable substances are apt todestroy the fireproof qualities of the liquid. It is an object of thepresent invention to make volatile chlorin-containing carbon compoundsof good solvent power for grease and oils and of less weight which shallbe sufliciently fireproof and of pleasanter odor; and to do this by asimple, cheap and ready method, using cheap materials.

In the present invention heavy petroleum oils, best of the type of thoseknown as fuel oils, are submitted to a brief heating in the neighborhoodof 700 'C. The temperature may be as low as 650 or as high as 850, butin general it is better between 700 and 750, and the heating should beso brief as to leave unchanged oil vapors in the sphere of reaction andemerging withthe gasproduced and as to remove the gas substantially asrapidly as formed. Any continued heating of the gas breaks it down togive tars, benzenoid bodies, etc. Advantageously, the oil may be passedat a rapid rate through a comparatively short length, say 30 to 70inches, of hot narrow tubing, such as'a half inch to an inch iron orcopper tube. The tubing should not be of greater internal diameter thanan inch or so since experience shows'unevenness of reaction and a disad-*vantageous character of the product where any portion of the chamberafforded by the channel in the oil treating conduit is more than an inchor so away from the heated from end to end. The presence of catalyticsis. of no particularadvantage. Absence of coky carbon is desirable.

Under these conditions a part of the oil breaks up into a mixture ofunsaturated gases and saturated gases while a portion of the oil remainsunchanged. The unsaturated gaseous compounds formed are of suchcharacter and in such mutual proportions as to give advantageous resultsin the present process. By passing the gaseous products from the sphereof reaction through a suitable. cooling arrangement the unchanged oilmay be separated out, carrying with it any light, oily cracked productsof the nature of gasolene. The excess of oil acts as an efficientscrubbing means here, removing from the gas any of these lightgasolene-like bodies which may have been formed. This is an importantfeature since any of these substances going forward with the gas willnot only waste .chlorin' but give products of a character unsuitable forthe present purposes. "ith heavy oils of the type of fuel oil used asthe raw material. and with a sufficient excess of oil, say 20 to percent., going through the sphere of reaction unchanged, ordinary aircooling of the gas will be sufficient to take out practically all of thecondensable non-gaseous matter. The heavy oil condensed out and carryinglight cracked products may be simply returned for admixture with freshoil and repassage. \Vith proper control of conditions it issubstantially tar free. proper operation, it better not to return theexcess oil. If desired, refrigerating means may be used beyond theair-cooling means. The cooled gases coming from the condenser arefitakendirectly into temperature-controlled chambers and admixed with chlorin.Mixing should be in the dark, that is opaque vessels should be used.

Diluents, such as nitrogen, carbon dioxid, products of combustion, etc.may be employed to slow down and regulate the chlorinating action ifdesired, but are not ordinarily necessary. The gas separated from theunpyrolyzed oil contains saturated gases like ethane, which are inthemselves good. diluents and aid in making the action regular.Substitution being obviated or restricted. in the present invention,gases like ethane are good diluents. steam in the mixture to any extentis ordinarily not advisable.

It is usually desirable to employ a little less chlorin than the gasesare capable of taking up easily. This saves substitutive reactions andcorrosion of the apparatus by chlorin and hydrochloric acid occurringfurther on.

The conditions under which the chlorination occurs are not a matter ofindifference.

Should tar form by im-' The use of- If the proper amount of chlorin (asshown by the bromin absorption test) is directly mixed with the gas andthe mixture kept cool, as by performingthe operation in an air cooledvessel, the reaction is comparatively slow; it starts quickly but soonslows .up and requires more time for completion than is practicable. Iflight strikes the reaction mixture, substitutive reactions take place.But by performing the reaction in a vessel kept at a temperature ofabout 100 C. by means of a boiling water jacket or steam jacket,reactionis good and ready, but even in the dark some substitution takesplace. Good results may however be so obtained using 'a subsequentpurifying step in treating the product. Onpassing the mixture of chlorinand oil gas, in about the proper proportions, through a lead tube in ahot water jacket, chlorination is complete in a foot or so of travel. Oncondensing the material and then distilling, its boiling point will atfirst be found between 80 and 00, but the thermometer quickly goes to150 C. On continuing the heating and distilling, the material comingover, when condensed and re-rectified, will however be found to have aboiling point between 100 and 150 C. Apparently'some of the HOl producedby substitutive reactions combines to form anadditive compound with theorganic chlorids; a compound having a boiling point or decomposing pointof about 150. Therefore, in directly chlorinating in the mannerdescribed, it is better to take the condensed liquid product and mixwith lime, soda, etc., before distilling. This decomposes the additivecompound and gives a distillate of the properties desired. In the stillthere remains a mixture of alkali chlorids and a heavy polymerizedmaterial similar to a heavy pulverized rubber.

The reaction just described, while convenient and giving a good product,nevertheless is somewhat wasteful of chlorin, since half of whatever isused in substitution is wasted. l urther. the organic chlorids formed insubstitution are not quite so desirable for my purposes. On the otherhand, the uninflammability of the product is good.

A better method of operations for most purposes is obtained bychlorinating in stages with removal of the products between stages. Afraction of the chlorin is added in each stage. This aids in preventingloss of chlorin by solution in the condensed chlorination product andconsequent removal from the sphere of activity. In a good embodiment ofmy invention, I take a cooled oil gas and mix it-with a fraction of thetotal chlorin required and run the mixture through a lead pipe immersedin a tub maintained at about 15 C. For a moderate capacity, the leadpipe may be 1.5

inch internal diameter, tapering down to a- 3 inch pipe. The totallength of the lead pipeshould be enough to cool the mixture of gases to15 C if they be warm and react readily onheating, or-to heat themto 15C. if they be cool on mixing. Beyond this pipe should be a trap wherethe liquid can 7 trapped off and the residual gas is now admixed withthe .rest of the chlorin required. The mixture is next run through athird length of lead'pipe in a bath maintained at about 100 C. Thisthird length may be quite short as the reaction is vig-' orous at thispoint. Beyond this reaction chamber the gases should be sent through agood condenser to remove the vapors of organic chlorids. The organicchlorids recoveredin all three stages'may be reunited and distilled.Nearly all the material will pass over between 75 or 80 and 105 andthismaterial is the new grease solvent of the present invention. In thefirst stage with the action at 15 C. any small amounts of triple bondhydrocarbons which may be present are chlorinated and also a majorfraction of the double bond hydrocarbons.

, In the second stage nearly all the residue of the double bondhydrocarbons are chlorinated. In the third stage the residue of theunsaturated compounds is acted on. If there be any amount of highmolecular hydrocarbons, such as propane, in the gas, they may undergosome substitution in the third stage, but. ordinarily with properpreparation of the gas there is not much of any saturated compound saveethane.

present and this does not chlorinate readily under the conditionsdescribed.

In the described three-stage operation there is ordinarily just aboutenough substitution occurring to compensate for the slightinflammability of the propylene chlorid;

If desired, of course the three fractions of the compound may berectified separately, but ordinarily there is not much use in this. Alittle lime or other alkali may be used in the rectification to takecare of any hydrochloric acid which may be formed. The residue in therectifying still may be further fractionated to regain high boilingfractions for other uses.

The residual gas going beyond the ch10- rinating apparatus and thecondensers may be burned or otherwise utilized. It may be chlorinated toform ethyl chlorid and other products by treatment with'chlorin inchambers exposed to actinic light such as that furnished by a mercuryarc, lamp.

The volatile fraction of the stated average boiling point is a thin,pleasantly smelling liquid of good solvent properties for oil and greaseand sufliciently volatile to enable its advantageous use for removinggrease spots and stains and for extracting oils and resins from variousvegetable and animal materials. It contains about per cent. chlorin andis substantially uninfiammable, just flashing a little but not ignitingon contact with a match. It is fairly stable and may be rectified andhandled in iron apparatus. While not as heavy as carbon tetrachlorid,weighing'about 10 pounds per gallon, it is equally eflicient gallon forgallon as a grease solvent. Other methods of breaking up oil to producea gas carrying unsaturated compounds may be used but the describedmethod is convenient and advantageous as producing a gas in which thevarious unsaturated compounds are in mutual proportions about right togive a chlorin-containing product of the boiling point and propertieshere desired without absorbing undue amounts of chlorin.

Crude petroleumsor fuel oils as free as possible from cyclichydrocarbons are the best for my purposes. If the gas is made asdescribed, cyclic hydrocarbons, such as benzol, are not produced (Ze nowto any detrimental extent since the low temperature and the presence ofthe excess of shielding oil prevent fargoing reactions at the expense ofethylene, etc., but where the oil contains such cyclic hydrocarbonsoriginally they reappear with the gas as benzol, toluol, etc. The excessof oil in condefisingtends to absorb these bodies but as the excess isusually returned for re-passage benzol accumulates in the system. Withoil containing aromatic compounds, therefore, efficient chilling meansor cold wash oil should be applied to the gas beyond the oil-removingmeans since it is desirable not to have benzol present in the gas goingto the chlorinating apparatus. Benzol is of course valuable and may beeasily recovered in the man- 'ner described but the yield of olefinicgas subsequent to removing the oil excess as this powder, compressedcommercial chlorin, etc.,-

I prefer to use chlorin directly from electrolytic cells as this appearsto be slightly more active than chlorin which has stood for a while. i

In the accompanying illustration I have shown, more or lessdiagrammatically, certain apparatus capable of use in the describedprocess. In this showing, the illustration is partly in vertical sectionand partly in elevation. I 7

Element 1 is a shallow flat retort, here shown as made of sheet iron,such as 3/18 inch boiler plate. At each end it is provided with aremovable closure 2 for opening and closing, as when coky carbon beginsto form. With the formation of coky carbon the operation should beinterrupted since this has a catalytic, self-increasing action upon thedecomposition of oil. A convenient type of retort is made by taking twoparallel 2-inch H angle irons each about 6 feet long for the sides andriveting sheet iron to them for the top and bottom plates. For gasifyinga couple of gallons of oil per minute, the retort may be about 3 feetwide. Oil or oil vapor is fed into it from main 3 through valved pipes4, of which there should be a plurality along the width of the retort.Heat isafforded by furnace chamber 5 on the top of which the retort isset. Gas is led out through a "plurality of pipes 6 (one is shown)leading to main 7 From this main depend a plurality of air-cooled pipes8 for condensing out heavy oil. These pipes go to main 9 having return10 for excess of 011.

"Gas is taken from-the main through 11 and passes through cooler 12,shown as submerged in tub 13. Chilled wash oil may be sent into contactwith the gas through valved inlet 14. The condensate of chilledcondensed materials, or of chilled oil carrying the same, escapesthrough-trap 15. The chilled gas passes through 16 where it is joined bya portion of chlorin from valved inlet 17 and through the worm 18 in tub19. This tub is kept filled with water at about 15 C. As shown, the tubeis of less section at its lower end 15 than at the worm 18. Condensedcarbon chlorids are taken off by a trap. 20. Y The residual gas passesonward through 21 and is joined by more chlorin from valved inlet 22.The mixture of gas and chlorin passes through worm 23 in 'tub 24. filledwith water maintained at about 50C. Condensing carbon chlorids areremoved through trap 25. Residual-gas passes onward through 26 and isjoined by the rest of the chlorin from valved inlet 27." The mixture ofgas and chlorin passes through worm 28 in tub 29' which may be full ofwater at 100 C. The

emerging mixture of gas and vapors passes through 30, past condenser 31.Condensed liquid is received in 32, while-uncondensed gases passbackward through conduit 33 to be used in heatin the furnace 5.

The carbon ch orids received in 20, 25

and 32 may be separately rectified and treated, but ordinarily it'is aswell to reunite them and rectify or otherwise treat as one body.Operating in the manner described,

all three portions will be substantially freegb of free chlorin, notonly obviating a waste of chlorin but preventing undesirable reactionsduring rectification and other treatment. To prevent chlorin remainingin the third or final condensate theprocess should ordinarily beconducted with a little less chlorin than corresponds to the unsaturatedhydrocarbons as shown by the bromin test. The carbon chlorids may berectified in any ordinary apparatus. The high-boiling residue may besaved until it accumulates ,and worked up for other purposes.

It is expedient with these carbon chlorids to agitate with or filterthrough a little fullers earth, bone black or similar agent.

Some of the Florida clays may be used for this purpose. This takes outcertain strong smelling by-products and renders the materialof betterodor. A little bone black or fullers earth sufiices for treatingrelatively 0o large quantities of material. This treatment with adeodorant may be before or after rectification.

In addition to its uses as a grease solvent,

the solvent of the present invention has many advantages in makingrubber cement. It may be used for this purpose alone or in admixturewith other solvents. The cement made with the present liquid has thegreat advantage of being uninflammable while the 10 solvent powers ofthe liquid for rubber are good.

The hydrocarbons removed at 15 by chilled wash oil may be recovered.They have characteristic properties which make them useful for a numberof purposes.

Owing to, the fact that double and triple bond hydrocarbons appear to bepresent, as

indicated above, the carbon chlorid mixture obtained as a productappears to be very complex, and to contain a notable fraction ofsubstances having four or six chlorin atoms per molecule.

A great advantage of the present process is the possibility which itoffers for complete chlorination of the olefins of oil gas together witha separate or conjoint recovery of the products of such chlorination asmay be desired. Of the olefins contained in oil gas cooled to ordinapy.temperature, the 13 greater part may be said to be ethylene,

propylene and less amounts of the butylenes,

together, in the event that the cooling was not complete or scrubbingwith oil was not thorough, more or less of the amylenes. These unitewith chlorin in the reverse of the order mentioned; that is, the5-carbon olefins unite more readily than the t-carbon and the l-carbonsunite more readily than the 3-carbon. The Q-earbon olefin or ethylenedoes not unite readily with chlorin in the cold; and it is a greatadvantage of this invention that ready chlorination of the ethylene maybe eilected with the obtaining of substantially pure products. In thestructure shown, and by the process described, the chlorination takingplace in the cooled tube, will be substantially only that of the higherolefins and propylene while in the second tube chlorination will bemainly of the propylene.

The ethylene chlorinated in the tube kept at the higher temperature and,if the operation is properly controlled, the liquid condensed. from thechlorinating operation in this tube is, or may be, nearly pure ethylenechlorid.

What I claim is:

1. The process of making a solvent which comprises cracking petroleumoil to yield a complex. mixture ofunsaturated hydrocarbon gases and agas adapted to serve as a diluent, removing condensable matter from saidgas and treating the residual gas with chlorin undertemperature-controlled conditions.

- 2. The process of making a solvent which comprises cracking petroleumoil to yield a complex mixture of unsaturated hydrocarbon gases and agas adapted to serve as a diluent, removing condensable matter from'saidgas and treating the residual gas with chlorin undertemperature-controlled conditions and chlorinating the residual gas,said chlorinating operation comprising a treatment of said gas withchlorin at about 100 C.

3. The process of making a solvent which comprises treating an oil gaswith chlorin in a plurality of stages, the chlorinated product of eachsuch stage being separately removed.

4. The process of making a solvent which comprises treating an oil gaswith chlorin in a plurality of stages under temperaturecontrolledconditions, the temperature in each successive stage being higher thanin the next preceding stage.

5. The process of making a solvent which comprises treating an oil gaswith chlorin in a plurality of stages under temperaturecontrolledconditions, the temperature in 6. The proce s of ma i g a solvent whichcomprises treating an oil gas with chlorin in a plurality of stagesunder temperaturemediate stage at an intermediate tempera-- ture. 7. Theprocess of making a solvent which comprises partially gasifying a heavyfuel toil, at a temperature high enough to form a large proportion ofmixed unsaturated carbon compounds and a diluent gas, condensing out theexcess of oil, and treating the resulting gas in a dark chamber withslightly less chlorin ,than corresponds to bromin absorption as shown bytest.

8. As a new composition of matter, a volatile substantiallyuninflammable liquid hav ing a boiling point between 75 and 105 C. witha major fraction distilling between 80 and 90, containing about percent. chlorin, having a specific gravity of about 1.2 and consistingmainly of ethylene and propylene chlorids.

9. The process of making a solvent which comprises cracking oil to yielda complex mixture of unsaturated hydrocarbon gases and a gas adapted toserve as a diluent, removing condensable matter from said gas, treatingwith chlorin under temperaturecontrolled conditions to obtain carbonchlo rids and treating the carbon chlorids with a deodorant. I

10. The process of making solvents which comprises mixing oil gas andchlorin.

11. As a new composition of matter, a volatile substantiallyuninflammable liquid having a minimum boiling point near C. and boilingofi' gradually till about 150 C. is reached near which pointdecomposition sets in, having a specific gravity not far removed from1.2, comprising ethylene and propylene chlorids, and distillable from analkaline substance to yield a similar liquidcboiling principally between75 and 105 12. The process of making solvents which comprises mixingchlorin with oil gas free from compounds condensable at ordinarytemperatures and regulating the reaction by controlling the temperaturethereof to'produce substantially only addition compounds.

13. The process of making a solvent which comprises treating an oil gasrich in unsaturated aliphatic series carbon compounds with chlorin underconditions adapted to limit the reaction largely to formation ofaddition products and separating the residual gas from the resultantsolvent, the gas being a mixture comprising one, two, and three bondhydrocarbons before said treating.

14; The process of making a solvent which comprises treating anoiL gasrich in unsaturated carbon compounds with chlorin conditions, saidchlorinating operationcomprising a treatment of said gas with chlorin atabout 100 C. and also a treatment at "the unsaturated hydrocarbonspresent.

15. A composition of matter comprising a complex mixture of chlorinatedhydrocarbons of the group formed by treating oil. gas which has beenproducedat a comparatively low temperature with chlorin, to producemainly additive compounds.

16. A composition of matter comprising a mixture of chlorinatedhydrocarbons having two, four and six chlorin atoms per molecule, anddistillable to produce a liquid boiling around 75 C. to 105 C. andcontaining about 70% of chlorin.

in the dark. under temperature controlled" 17. The process of making asolvent which comprises the chlorination of oil gas in stages, atsuccessively higher temperatures' 18. The process of making a solventwhich comprises the complete chlorination of oil gas in stages adaptedto selectively chlorinate the compounds therein.

19. The process of making a solvent which comprises reacting upon oilgaswith chlorin GAIL MERSEREAU.

Witnesses:

F LORENOE MAUs, EDWARD GoRnoN.

'in an amount slightly less than that corre- 1

